JP5614462B2 - Gas diffusion electrode base material for fuel cell, membrane electrode assembly, and fuel cell - Google Patents

Description

  The present invention relates to a gas diffusion electrode substrate suitably used for a fuel cell, particularly a polymer electrolyte fuel cell. More specifically, it has excellent flooding resistance and plugging resistance, and also has excellent dry-up resistance, and can exhibit high power generation performance over a wide temperature range from low temperature to high temperature. In addition, it has mechanical properties, electrical conductivity, and thermal conductivity. The present invention relates to a gas diffusion electrode substrate having excellent properties.

  A polymer electrolyte fuel cell that supplies a fuel gas containing hydrogen to the anode and an oxidizing gas containing oxygen to the cathode to obtain an electromotive force by an electrochemical reaction occurring at both electrodes is generally a separator, gas diffusion An electrode base material, a catalyst layer, an electrolyte membrane, a catalyst layer, a gas diffusion electrode base material, and a separator are laminated in order. The gas diffusion electrode base material has high gas diffusibility for diffusing the gas supplied from the separator to the catalyst layer, high drainage for discharging water generated by the electrochemical reaction to the separator, and the generated current High electrical conductivity is required to extract the carbon, and electrode base materials made of carbon fiber or the like are widely used.

  However, as problems, (1) when the polymer electrolyte fuel cell is operated in a relatively low temperature of less than 70 ° C. and in a high current density region, the electrode substrate is clogged with a large amount of liquid water, and the supply of fuel gas As a result, the power generation performance is reduced as a result of shortage (hereinafter referred to as flooding). (2) When a polymer electrolyte fuel cell is operated at a relatively low temperature of less than 70 ° C. and in a high current density region, a large amount is generated. The problem is that the power generation performance is instantaneously reduced (hereinafter referred to as plugging) (3) 80 as a result of the gas flow (hereinafter referred to as flow path) of the separator being blocked by the liquid water to be supplied and the fuel gas supply being insufficient. When operating at a relatively high temperature of ℃ or higher, the electrolyte membrane is dried by water vapor diffusion, and proton conductivity is reduced, resulting in a problem that power generation performance is reduced (hereinafter referred to as dry-up). To have. Many efforts have been made to solve these problems (1) to (3).

  Patent Document 1 proposes a gas diffusion electrode base material in which a microporous portion made of carbon black and a hydrophobic resin is formed on the catalyst layer side of the electrode base material. According to the fuel cell using this gas diffusion electrode substrate, since the microporous portion forms a small pore structure having water repellency, the discharge of liquid water to the cathode side is suppressed, and the flooding tends to be suppressed. It is in. Further, since the generated water is pushed back to the electrolyte membrane side (hereinafter referred to as reverse diffusion), the electrolyte membrane tends to be wet and dry-up tends to be suppressed.

  Patent Documents 2 and 3 propose a fuel cell using a gas diffusion electrode base material in which microporous portions made of carbon black and a hydrophobic resin are formed on both surfaces of the electrode base material. According to the fuel cell using this gas diffusion electrode base material, the microporous portion on the separator side is smooth and has high water repellency, so that liquid water does not easily stay in the flow path, and plugging is suppressed. Further, the reverse diffusion of the generated water is promoted by the microporous portion on the catalyst layer side, and in addition, the water vapor diffusion is suppressed by the microporous portion on the separator side. As a result, the electrolyte membrane is wetted and dry-up is suppressed.

  Patent Document 4 proposes a gas diffusion electrode base material in which a microporous portion made of carbon black and a hydrophobic resin is formed on the catalyst layer side of the electrode base material, and the microporous portion has an island shape or a lattice shape. According to the fuel cell using this gas diffusion electrode base material, it is supposed that the reaction gas can be smoothly supplied to the catalyst layer from the void portion without the microporous portion.

JP 2000-123842 A Japanese Patent Laid-Open No. 9-245800 JP 2008-293937 A JP 2004-164903 A

  However, the technique described in Patent Document 1 has a problem that suppression of flooding and dry-up is still insufficient, and plugging is not improved at all.

  Further, the techniques described in Patent Documents 2 and 3 have a problem that flooding becomes significant because drainage from the electrode base material to the separator is hindered by the microporous portion on the separator side.

  Further, the technique described in Patent Document 4 has a problem that since there is a void portion without a microporous portion, the back diffusion of generated water is insufficient, and it is easy to dry up. Furthermore, since the contact surface between the microporous portion and the catalyst layer is not smooth, there is a problem that the contact electrical resistance increases and the power generation performance from low temperature to high temperature decreases.

  Many such techniques have been proposed, but a gas diffusion electrode base material having excellent flooding resistance and plugging resistance and excellent dry-up resistance has not yet been found.

  Therefore, the object of the present invention is excellent in flooding / plugging resistance, excellent in dry-up resistance, and capable of expressing high power generation performance over a wide temperature range from low temperature to high temperature. The object is to provide a gas diffusion electrode substrate having excellent thermal conductivity.

  As a result of intensive studies, the present inventors have found that in the gas diffusion electrode substrate in which the microporous portion is formed on both surfaces of the electrode substrate, the area ratio of the microporous portion on one side is appropriately small, and the microporous portion on the opposite surface side It has been found that by increasing the area ratio of the porous portion, the drainage from the electrode base material can be prevented from being inhibited without impairing the effect of suppressing plugging and dry-up, and the flooding resistance can be greatly improved. As a result, it is possible to achieve both flood resistance, plucking resistance, and dry-up resistance, thereby completing the present invention.

  The microporous portion on one side of the electrode substrate is referred to as a microporous portion [A], and the microporous portion on the opposite surface side is referred to as a microporous portion [B].

In the gas diffusion electrode substrate of the present invention, the microporous portion [A], the electrode substrate, and the microporous portion [B] are arranged in this order, and the area ratio of the microporous portion [A] is 5 to 70. % of a range state, and are within the scope area ratio of 80% to 100% of the microporous portion [B], or microporous portion [a] is a pattern, microporous portion [a] is a micro or porous portion is formed by provided a large number on the surface of the electrode substrate, a microporous portion [a] is characterized random shapes der Rukoto.
However, the area ratio is the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate.

  In the conventional technology, only the entire surface of the microporous part was applied to both sides, and the idea of controlling the microporous part on both sides separately to achieve both flooding resistance, plugging resistance and dry-up resistance was found. It is not easily derived.

  Moreover, the manufacturing method of the gas diffusion electrode base material of the present invention employs the following means. That is, the method for producing a gas diffusion electrode base material, wherein the microporous portion [A] is formed by screen printing or gravure printing on the surface opposite to the surface having the microporous portion [B] of the electrode base material. It is.

  In order to solve the above problems, the membrane electrode assembly of the present invention has a catalyst layer on both sides of an electrolyte membrane, and further has the fuel cell gas diffusion electrode substrate outside the catalyst layer. This fuel cell has separators on both sides of the membrane electrode assembly.

That is, the present invention comprises the following elements.
(1) The microporous part [A], the electrode substrate, and the microporous part [B] are arranged in this order, and the area ratio of the microporous part [A] is in the range of 5 to 70%, Ri range der area ratio of 80% to 100% of the microporous portion [B], the microporous portion [a] is the fuel cell gas diffusion electrode substrate, characterized that you have to form a pattern.
However, the area ratio is the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate.
(2) The microporous part [A], the electrode substrate, and the microporous part [B] are arranged in this order, and the area ratio of the microporous part [A] is in the range of 5 to 70%, The area ratio of the microporous portion [B] is in the range of 80 to 100%, and the microporous portion [A] is formed by providing a large number of microporous portions on the surface of the electrode substrate. A gas diffusion electrode base material for a fuel cell.
However, the area ratio is the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate.
(3) The microporous part [A], the electrode substrate, and the microporous part [B] are arranged in this order, and the area ratio of the microporous part [A] is in the range of 5 to 70%, A gas diffusion electrode substrate for a fuel cell, wherein the area ratio of the microporous part [B] is in the range of 80 to 100%, and the microporous part [A] has a random shape.
However, the area ratio is the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate.
( 4 ) The gas diffusion electrode for a fuel cell according to any one of (1) to (3), wherein the microporous portion [A] is composed of an assembly of linear microporous portions having an average line width of 0.1 to 5 mm. Base material.
( 5 ) The gas diffusion electrode substrate for a fuel cell according to (1) or (2) , wherein the microporous portion [A] has a stripe shape or a lattice shape.
( 6 ) A method for producing a gas diffusion electrode substrate for a fuel cell according to any one of (1) to ( 5 ), wherein the microporous portion [A] is formed by screen printing or gravure printing. Of manufacturing a gas diffusion electrode substrate for use.
( 7 ) A membrane electrode assembly having a catalyst layer on both sides of the electrolyte membrane and further having a gas diffusion electrode substrate outside the catalyst layer, wherein at least one of the gas diffusion electrode substrates is (1) to ( 5 ) A membrane electrode assembly, which is the gas diffusion electrode substrate according to any one of ( 5 ).
( 8 ) The membrane electrode assembly according to ( 7 ), wherein the microporous portion [B] of the gas diffusion electrode substrate is in contact with the catalyst layer.
( 9 ) A fuel cell having separators on both sides of the membrane electrode assembly according to ( 8 ).

  Since the gas diffusion electrode substrate of the present invention has a microporous portion [A] and a microporous portion [B], the plugging resistance and the dry-up resistance are high, and the area ratio of the microporous portion [A] is 5 to 5. Since it is within the range of 70%, the drainage from the electrode substrate is good and the flooding resistance is high. Since carbon paper or the like can be used for the electrode base material, the gas diffusion electrode base material of the present invention has good mechanical strength, electrical conductivity, and thermal conductivity. When the gas diffusion electrode substrate of the present invention is used, high power generation performance can be expressed over a wide temperature range from low temperature to high temperature.

It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is one aspect | mode of the pattern of the microporous part [A] of this invention. It is a schematic diagram (sectional drawing) which shows the structural example of the gas diffusion electrode base material of this invention. It is a schematic diagram (bird's eye view seen from the microporous part [A] side) which shows the example of composition of the gas diffusion electrode substrate of the present invention. It is a schematic diagram (bird's eye view seen from the microporous part [A] side) which shows the example of composition of the gas diffusion electrode substrate of the present invention. It is a schematic diagram (sectional drawing) which shows the structural example of the membrane electrode assembly of this invention. In this invention, it is a schematic diagram (sectional drawing) which shows the structural example of a membrane electrode assembly especially preferable. It is a schematic diagram (cross-sectional view) showing a configuration example of the fuel cell of the present invention.

  In the gas diffusion electrode substrate of the present invention, the microporous part [A], the electrode base material, and the microporous part [B] are arranged adjacently in this order. Hereinafter, each component will be described. In the present invention, a substrate made of only carbon paper and not provided with a microporous portion is referred to as an “electrode substrate”, and a substrate provided with a microporous portion on an electrode substrate is referred to as a “gas diffusion electrode substrate”. Called.

  First, the electrode base material which is a component of the present invention will be described.

  In the present invention, the electrode base material has a high gas diffusibility for diffusing the gas supplied from the separator to the catalyst, and a high drainage property for discharging the water generated along with the electrochemical reaction to the separator. High conductivity is required to extract current. For this reason, it is preferable to use a porous body having conductivity and an average pore diameter of 10 to 100 μm. More specifically, for example, it is preferable to use a porous body containing carbon fibers such as a carbon fiber woven fabric, a carbon fiber papermaking body, and a carbon fiber nonwoven fabric, a porous metal body such as a fired sintered metal, a metal mesh, and an expanded metal. Among them, it is preferable to use a porous body containing carbon fiber because of its excellent corrosion resistance, and furthermore, because of its excellent property of absorbing dimensional change in the thickness direction of the electrolyte membrane, that is, “spring property”, carbon fiber. It is preferable to use a base material obtained by binding a paper body with a carbide, that is, “carbon paper”. In the present invention, a substrate formed by binding a carbon fiber papermaking body with a carbide is usually obtained by impregnating a carbon fiber papermaking body with a resin and carbonizing it, as will be described later.

  Examples of the carbon fiber include polyacrylonitrile (PAN) -based, pitch-based, and rayon-based carbon fibers. Of these, PAN-based and pitch-based carbon fibers are preferably used in the present invention because of excellent mechanical strength.

  In the carbon fiber of the present invention, the average diameter of the single fibers is preferably in the range of 3 to 20 μm, and more preferably in the range of 5 to 10 μm. When the average diameter is 3 μm or more, the pore diameter is increased, drainage is improved, and flooding can be suppressed. On the other hand, when the average diameter is 20 μm or less, the water vapor diffusibility becomes small, and dry-up can be suppressed. Moreover, it is preferable to use two or more types of carbon fibers having different average diameters because the surface smoothness of the electrode substrate can be improved.

  Here, the average diameter of the single fiber in the carbon fiber is taken with a microscope such as a scanning electron microscope, the carbon fiber is magnified 1000 times or more, and 30 different single fibers are randomly selected. The diameter was measured and the average value was obtained. As a scanning electron microscope, S-4800 manufactured by Hitachi, Ltd. or an equivalent thereof can be used.

  In the carbon fiber of the present invention, the average length of single fibers is preferably in the range of 3 to 20 mm, and more preferably in the range of 5 to 15 mm. When the average length is 3 mm or more, the electrode base material is preferable because it has excellent mechanical strength, electrical conductivity, and thermal conductivity. On the other hand, when the average length is 20 mm or less, the dispersibility of carbon fibers during papermaking is excellent, and a homogeneous electrode substrate is obtained, which is preferable. Carbon fibers having such an average length can be obtained by a method of cutting continuous carbon fibers into a desired length.

  Here, the average length of the carbon fiber is taken with a microscope such as a scanning electron microscope, the carbon fiber is magnified 50 times or more, and 30 different single fibers are selected at random. Is measured and the average value is obtained. As a scanning electron microscope, S-4800 manufactured by Hitachi, Ltd. or an equivalent thereof can be used. In addition, although the average diameter and average length of the single fiber in carbon fiber are normally measured by observing the carbon fiber directly about the carbon fiber used as a raw material, you may observe and measure an electrode base material.

In the present invention, it is preferable that the density of the electrode substrate is in the range of 0.2-0.4 g / cm ^3, more preferably in the range of 0.22~0.35g / cm ^3, further Is preferably in the range of 0.24 to 0.3 g / cm ³ . When the density is 0.2 g / cm ³ or more, the water vapor diffusibility is small, and dry-up can be suppressed. Further, the mechanical properties of the electrode substrate are improved, and the electrolyte membrane and the catalyst layer can be sufficiently supported. In addition, the conductivity is high, and the power generation performance is improved at both high and low temperatures. On the other hand, when the density is 0.4 g / cm ³ or less, drainage is improved and flooding can be suppressed. The electrode base material having such a density can be obtained by controlling the carbon fiber basis weight in the pre-impregnated body, the blending amount of the resin component with respect to the carbon fiber, and the thickness of the electrode base material in the production method described later. In the present invention, a paper body containing carbon fibers impregnated with a resin composition is referred to as a “pre-impregnated body”. In particular, it is effective to control the carbon fiber basis weight in the pre-impregnated body and the blending amount of the resin component to the carbon fiber. Here, a low-density substrate is obtained by reducing the carbon fiber basis weight of the pre-impregnated body, and a high-density substrate is obtained by increasing the carbon fiber basis weight. Moreover, a low density base material is obtained by reducing the compounding quantity of the resin component with respect to carbon fiber, and a high density base material is obtained by increasing the compounding quantity of the resin component. Moreover, a low density base material is obtained by increasing the thickness of the electrode base material, and a high density base material is obtained by reducing the thickness.

  Here, the density of the electrode base material is obtained by dividing the basis weight (mass per unit area) of the electrode base material weighed using an electronic balance by the thickness of the electrode base material when pressed with a surface pressure of 0.15 MPa. Can be obtained.

  In the present invention, the pore diameter of the electrode substrate is preferably in the range of 30 to 80 μm, more preferably in the range of 40 to 75 μm, and further preferably in the range of 50 to 70 μm. When the pore diameter is 30 μm or more, drainage can be improved and flooding can be suppressed. When the pore diameter is 80 μm or less, the conductivity is high, and the power generation performance is improved at both high and low temperatures. In order to design within such a pore diameter range, it is effective to include both carbon fibers having an average single fiber diameter of 3 μm to 8 μm and carbon fibers having an average single fiber diameter exceeding 8 μm.

  Here, the pore diameter of the electrode substrate is obtained by determining the peak diameter of the pore diameter distribution obtained by measuring in the measurement pressure range of 6 kPa to 414 MPa (pore diameter 30 nm to 400 μm) by mercury porosimetry. When a plurality of peaks appear, the peak diameter of the highest peak is adopted. As a measuring device, Autopore 9520 manufactured by Shimadzu Corporation or an equivalent product thereof can be used.

  In this invention, it is preferable that the thickness of an electrode base material is 60-200 micrometers. More preferably, it is 70-160 micrometers, More preferably, it is 80-110 micrometers. When the thickness of the electrode substrate is 60 μm or more, the mechanical strength becomes high and handling becomes easy. When the thickness is 200 μm or less, the cross-sectional area of the electrode base material is reduced, and the amount of gas through which the liquid water flows in the separator channel increases, so that plugging can be suppressed. Further, the path for draining is shortened, and flooding can be suppressed.

  Here, the thickness of the electrode base material can be determined using a micrometer in a state where the surface pressure is 0.15 MPa.

  Next, the microporous parts [A] and [B], which are constituent elements of the present invention, will be described.

The microporous portions [A] and [B] are respectively provided on both sides of the electrode base material as shown in FIG. In the present invention, it is not necessary that the entire surface of the electrode substrate is covered with the microporous portion. That is, as shown in FIGS. 13 and 14, at least a part of the surface of the electrode substrate may be covered with the microporous portion. Here, the microporous portion refers to a porous body having pores therein. In FIG. 13 and FIG. 14, the microporous portion [A] is formed by providing a large number of such microporous portions on the surface of the electrode base material. Of course, as long as the microporous portion [B] satisfies the numerical range of the area ratio to be described later, the microporous portion [B] may take an embodiment as shown in FIGS.

The area ratio of the microporous portion [A] needs to be within a range of 5 to 70%, and the area ratio of the microporous portion [B] needs to be within a range of 80 to 100%. Here, the area ratio refers to the ratio (%) of the area covered with the microporous portion to the area of the electrode base material on one surface of the gas diffusion electrode base material, and is calculated by the following equation.
Area ratio (%) = area covered with microporous portion / area of electrode substrate × 100
Here, the area ratio can be obtained, for example, according to the following procedure.

  First, the surface of one side of the gas diffusion electrode substrate is photographed with a digital camera, a digital microscope or the like to obtain an image. Here, as a digital microscope, a digital HD microscope VH-7000 manufactured by Keyence Corporation or an equivalent thereof can be used. It is preferable to select 10 different places from the gas diffusion electrode base material at random, and take a photograph in a range of about 3 cm × 3 cm. Next, the obtained image is binarized into a portion covered with the microporous portion and a portion not covered with the microporous portion. There are various methods of binarization, and when the part covered with the microporous part and the part not covered with the microporous part can be clearly discriminated, a method of visually discriminating may be adopted, In the present invention, it is preferable to employ a method using image processing software or the like. Here, Adobe Photoshop (registered trademark) manufactured by Adobe System can be used as the image processing software. In each image, the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate (the sum of the areas covered with the microporous portion and the portion not covered with the microporous portion) Is calculated and the average value is obtained.

  On the other hand, when measuring after making it a state of a membrane electrode assembly etc. using a gas diffusion electrode base material, an area ratio can be calculated according to the following procedure. First, with a microscope such as a scanning electron microscope, 100 different locations are selected at random from the cross section of the gas diffusion electrode substrate, and each image is magnified at a magnification of about 40 times to obtain an image. Here, S-4800 manufactured by Hitachi, Ltd. or an equivalent product can be used as the scanning electron microscope. Next, using the obtained images, the ratio of the area in which the surface of the electrode substrate is covered with the microporous portion with respect to each of the microporous portion [A] and the microporous portion [B] in each image. (%) Is measured and the average value is obtained.

  When the microporous portion [A] has an area ratio of 5 to 70%, liquid water is less likely to stay in the flow path, and plugging can be suppressed. At the same time, since the area ratio is small, it is possible to prevent obstructing the direct gas diffusion and drainage, and greatly improve the flooding resistance. The area ratio of the microporous portion [A] is more preferably 10 to 60%, and further preferably 20 to 40%. When the area ratio of the microporous portion [A] is 70% or less, the ratio of the microporous portion [A] covering the surface of the electrode base material is not too high, and surface gas diffusion and drainage are ensured, and flooding is performed. Can be suppressed. When the area ratio of the microporous portion [A] is 5% or more, liquid water does not easily stay in the flow path, plugging can be suppressed, and back-up of generated water is promoted, so that dry-up is also suppressed. .

  Since the area ratio of the microporous portion [B] is 80 to 100%, it is possible to promote the reverse diffusion of the generated water, so that the dry-up can be suppressed. In addition, when a membrane electrode assembly is configured using the gas diffusion electrode substrate, and further a fuel cell is configured using the membrane electrode assembly, the contact between the gas diffusion electrode substrate and the catalyst layer or the separator The area is increased, and the contact electrical resistance can be reduced. This is because the surface irregularities of the electrode base material are covered and smoothed by the microporous portion [B].

  The microporous part [A] and the microporous part [B] are preferably made of carbonaceous powder and a hydrophobic resin. In other words, the microporous portion constituting the microporous portion [A] and the microporous portion [B] is preferably made of carbonaceous powder and a hydrophobic resin. Examples of the carbonaceous powder include carbon black, graphite powder, carbon nanofiber, and carbon fiber milled fiber. Among them, it is preferable to use carbon black because it is easy to handle. The classification of carbon black includes furnace black, channel black, acetylene black, thermal black and the like. Examples of hydrophobic resins include polychlorotrifluoroethylene resin (PCTFE), polytetrafluoroethylene resin (PTFE), polyvinylidene fluoride resin (PVDF), a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), and tetrafluoro. Examples thereof include fluorine resins such as a copolymer of ethylene and perfluoropropyl vinyl ether (PFA) and a copolymer of tetrafluoroethylene and ethylene (ETFE).

  The microporous part [A] and the microporous part [B] (and the microporous part constituting them) may contain 1 to 70 parts by mass of a hydrophobic resin per 100 parts by mass of the carbonaceous powder. Preferably, 5 to 60 parts by mass is blended. When the blending amount of the hydrophobic resin is 1 part by mass or more, the microporous part [A] and the microporous part [B] are preferable because they have excellent mechanical strength. On the other hand, when it is 70 parts by mass or less, the microporous part [A] and the microporous part [B] are preferable because they have excellent conductivity and thermal conductivity.

  The thickness of the microporous part [A] is preferably in the range of 1 to 20 μm, more preferably 8 to 16 μm. When the thickness is 1 μm or more, the surface of the microporous portion [A] becomes smooth, and when the microporous portion [A] is used facing the separator as a gas diffusion electrode base material of a fuel cell, the separator and the gas diffusion electrode base The contact electrical resistance with the material can be reduced. Moreover, it is preferable for it to be 20 μm or less because the electrical resistance of the microporous portion [A] can be reduced. The microporous portion [B] preferably has a thickness of 1 to 50 μm, and more preferably 10 to 30 μm. When the thickness is 1 μm or more, the promotion of the reverse diffusion of generated water becomes remarkable, and the surface of the microporous portion [A] becomes smooth, and the microporous portion [B] is used as a catalyst for the gas diffusion electrode substrate of the fuel cell. When used toward the layer side, the contact electrical resistance between the catalyst layer and the gas diffusion electrode substrate can be reduced. It is preferable for the thickness to be 50 μm or less because the electrical resistance of the microporous portion [B] can be kept small.

  The microporous portion [A] may have the same composition as the microporous portion [B] or may have a different composition. When the microporous part [A] has a different composition, specifically, the particle size of the carbon black is made smaller than that of the microporous part [B], the blending amount of the hydrophobic resin is increased, It is preferable to make the microporous portion [A] denser than the microporous portion [B] by adding a thermosetting resin. Specifically, it is preferable to make the porosity of the microporous [A] smaller than the microporous part [B]. As a result, even if the area ratio of the microporous portion [A] is reduced, liquid water is less likely to stay in the flow path, and it is possible to suppress plugging and to prevent drainage from the electrode base material. Can improve sex.

  Hereinafter, preferred embodiments of the microporous portion [A] in the present invention will be described with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

In one aspect of the present invention, the microporous portion [A] is that form a pattern. In the present invention, a pattern or pattern is a pattern that is repeated at a constant period. It is preferable that there is a repetition period in an area of 100 cm ² or less, and it is more preferable that there is a repetition period in an area of 10 cm ² or less. Since the period is small, in-plane performance variations such as conductivity and drainage can be reduced. When a plurality of gas diffusion electrode base materials are prepared, the presence or absence of a period may be confirmed by comparing between sheets. Examples of patterns include lattices, stripes, concentric circles, islands, and the like, for example, as shown in FIGS. 1 to 11 (in FIGS. 1 to 11, black portions indicate portions where microporous portions are provided. The white portion indicates a portion where no microporous portion is provided). Moreover, when the flow path of a separator is a pattern like the white part of FIG. 3, it is preferable that a microporous part [A] is a pattern corresponding to the rib part of a separator like the black part of FIG. By arranging the microporous portion [A] having a pattern corresponding to the rib portion on the electrode base material, it is possible to increase the effect of the path cut from the flow channel to the adjacent flow channel. The plugging property is improved.
In another aspect of the present invention, the microporous portion [A] has a random shape.

The microporous portion [A] is preferably composed of an assembly of linear microporous portions having an average line width of 0.1 to 5 mm, and is preferably composed of an assembly of linear microporous portions of 0.1 to 2 mm. More preferably, it is preferably composed of an assembly of linear microporous portions of 0.1 to 1 mm. In the present invention, the line refers to a line having a width of 0.1 mm or more and an aspect ratio of 2 or more. Here, the aspect ratio refers to a ratio of line length (mm) to width (mm) ([line length] / [line width]). By using an aggregate of linear microporous portions having an average line width of 0.1 to 5 mm as the microporous portion [A], in-plane variation of the plugging suppression effect can be reduced. When the line width is 0.1 mm or more, liquid water hardly stays in the flow path, and the effect of suppressing plugging is enhanced. When the average line width is 5 mm or less, the in-plane conductivity and drainage variation can be reduced. Among the aggregate of lines, a lattice shape or a stripe shape is preferable. In the present invention, a “lattice” is a collection of lines and refers to a pattern having a portion (intersection) where the lines intersect, and a “stripe” is a collection of lines and the lines do not cross each other. Refers to the pattern. Among the lattices, those in which the lines are straight and the crossing angle is 90 degrees are particularly preferable because the in-plane performance variation of the gas diffusion electrode substrate can be suppressed to be small. Moreover, when the number of intersections is 10 or more per 1 cm ² , the variation can be greatly reduced, which is more preferable. Among the stripes, a straight line is particularly preferable because it can suppress in-plane performance variations of the gas diffusion electrode substrate.

  That is, in the present invention, the microporous portion [A] preferably forms a pattern of the microporous portion on the electrode substrate, and the shape of the pattern is the above-described lattice shape or stripe shape. Is particularly preferred.

  Next, a method suitable for obtaining the gas diffusion electrode substrate of the present invention will be specifically described.

<Paper making body and method for producing paper making body>
In the present invention, in order to obtain a papermaking body containing carbon fibers, a wet papermaking method in which carbon fibers are dispersed in a liquid and a dry yarn making method in which the fibers are dispersed in air are used. Of these, the wet papermaking method is preferably used because of its excellent productivity.

  In the present invention, for the purpose of improving the drainage and gas diffusibility of the electrode substrate, paper can be made by mixing carbon fibers with organic fibers. As the organic fiber, polyethylene fiber, vinylon fiber, polyacetal fiber, polyester fiber, polyamide fiber, rayon fiber, acetate fiber, or the like can be used.

  In the present invention, an organic polymer can be included as a binder for the purpose of improving the form retainability and handling of the papermaking body. Here, as the organic polymer, polyvinyl alcohol, polyvinyl acetate, polyacrylonitrile, cellulose or the like can be used.

  The paper body in the present invention is preferably in the form of a sheet in which carbon fibers are randomly dispersed in a two-dimensional plane for the purpose of maintaining in-plane conductivity and thermal conductivity isotropic.

  The pore size distribution obtained from the papermaking body can be formed to a size of about 20 to 500 μm, although it is affected by the carbon fiber content and dispersion state.

In the present invention, paper body is preferably the basis weight of the carbon fibers is in the range of 10 to 60 g / ^{m 2,} and more preferably in the range of 20 to 50 g / ^{m 2.} It is preferable that the basis weight of the carbon fiber is 10 g / m ² or more because the electrode base material has excellent mechanical strength. It is preferable that it is 60 g / m ² or less because the electrode base material has excellent gas diffusibility and drainage. In addition, when bonding a plurality of paper bodies, it is preferable that the basis weight of the carbon fibers after the bonding is in the above range.

Here, the weight per unit area of the carbon fiber in the electrode base material is the weight of the residue obtained by removing the organic matter by holding the paper body cut to 10 cm square in an electric furnace at a temperature of 450 ° C. for 15 minutes in a nitrogen atmosphere. , Divided by the area of the paper body (0.1 m ² ).

<Impregnation of resin composition>
In the present invention, as a method of impregnating a paper composition containing carbon fibers with a resin composition, a method of immersing a papermaking article in a solution containing a resin composition, a method of applying a solution containing a resin composition to a papermaking article, a resin For example, a method of transferring a film made of the composition on a paper body is used. Especially, since productivity is excellent, the method of immersing a papermaking body in the solution containing a resin composition is used preferably.

  The resin composition used in the present invention is preferably one that is carbonized upon firing to become a conductive carbide. A resin composition means what added the solvent etc. to the resin component as needed. Here, the resin component includes a resin such as a thermosetting resin, and further includes additives such as a carbon-based filler and a surfactant as necessary.

  In the present invention, more specifically, the carbonization yield of the resin component contained in the resin composition is preferably 40% by mass or more. It is preferable that the carbonization yield is 40% by mass or more because the electrode base material has excellent mechanical properties, electrical conductivity, and thermal conductivity.

  In the present invention, examples of the resin constituting the resin component include thermosetting resins such as phenol resin, epoxy resin, melamine resin, and furan resin. Of these, a phenol resin is preferably used because of its high carbonization yield. Moreover, as an additive added to a resin component as needed, a carbon-type filler can be included in order to improve the mechanical characteristics, electroconductivity, and thermal conductivity of an electrode base material. Here, as the carbon-based filler, carbon black, carbon nanotube, carbon nanofiber, milled fiber of carbon fiber, graphite, or the like can be used.

  The resin composition used in the present invention can use the resin component obtained by the above-described configuration as it is, and if necessary, contains various solvents for the purpose of improving the impregnation property to the papermaking body. Can do. Here, methanol, ethanol, isopropyl alcohol, or the like can be used as the solvent.

  The resin composition in the present invention is preferably in a liquid state at 25 ° C. and 0.1 MPa. When it is liquid, it is preferable because the paper body has excellent impregnation properties and the electrode base material has excellent mechanical properties, electrical conductivity, and thermal conductivity.

  In this invention, it is preferable to impregnate a resin component 30-400 mass parts with respect to 100 mass parts of carbon fibers, and it is more preferable to impregnate 50-300 mass parts. When the impregnation amount of the resin component is 30 parts by mass or more, the electrode base material is preferable because it has excellent mechanical properties, electrical conductivity, and thermal conductivity. On the other hand, when the impregnation amount of the resin component is 400 parts by mass or less, the electrode base material is preferable because it has excellent gas diffusibility.

<Lamination and heat treatment>
In the present invention, after a pre-impregnated body impregnated with a resin composition is formed on a papermaking body containing carbon fibers, prior to carbonization, the pre-impregnated body can be bonded or heat-treated.

  In the present invention, a plurality of pre-impregnated bodies can be bonded together for the purpose of setting the electrode substrate to a predetermined thickness. In this case, a plurality of pre-impregnated bodies having the same properties can be bonded together, or a plurality of pre-impregnated bodies having different properties can be bonded together. Specifically, a plurality of pre-impregnated bodies having different average diameters and average lengths of carbon fibers, carbon fiber basis weight of the papermaking body, impregnation amount of the resin component, and the like can be bonded together.

  In the present invention, the pre-impregnated body can be heat-treated for the purpose of thickening and partially cross-linking the resin composition. As a heat treatment method, a method of blowing hot air, a method of heating with a hot plate such as a press device, a method of heating with a continuous belt, or the like can be used.

<Carbonization>
In the present invention, after impregnating the paper composition containing carbon fibers with the resin composition, firing is performed in an inert atmosphere in order to carbonize the paper composition. For this firing, a batch type heating furnace can be used, or a continuous type heating furnace can be used. The inert atmosphere can be obtained by flowing an inert gas such as nitrogen gas or argon gas in the furnace.

  In the present invention, the maximum firing temperature is preferably in the range of 1300 to 3000 ° C, more preferably in the range of 1700 to 3000 ° C, and further in the range of 1900 to 3000 ° C. preferable. When the maximum temperature is 1300 ° C. or higher, the carbonization of the resin component proceeds, and the electrode base material is preferably excellent in conductivity and thermal conductivity. On the other hand, the maximum temperature of 3000 ° C. or lower is preferable because the operating cost of the heating furnace is reduced.

  In the present invention, the firing rate is preferably in the range of 80 to 5000 ° C./min for firing. A temperature increase rate of 80 ° C. or higher is preferable because productivity is excellent. On the other hand, when the temperature is 5000 ° C. or lower, the carbonization of the resin component gradually proceeds and a dense structure is formed. Therefore, the electrode base material is preferably excellent in conductivity and thermal conductivity.

  In the present invention, the carbonized paper impregnated with a resin composition and then carbonized is referred to as a “carbon fiber fired body”.

<Water repellent finish>
In the present invention, the carbon fiber fired body is preferably subjected to water repellent treatment for the purpose of improving drainage. The water-repellent finish can be performed by applying a hydrophobic resin to the carbon fiber fired body and heat-treating it. The application amount of the hydrophobic resin is preferably 1 to 50 parts by mass, and more preferably 3 to 40 parts by mass with respect to 100 parts by mass of the carbon fiber fired body. When the application amount of the hydrophobic resin is 1 part by mass or more, the electrode substrate is preferable because it has excellent drainage. On the other hand, when the amount is 50 parts by mass or less, the electrode base material is preferably excellent in conductivity.

  In the present invention, the carbon fiber fired body corresponds to an “electrode substrate”. As described above, the carbon fiber fired body is subjected to water-repellent finishing as necessary, but in the present invention, the carbon fiber fired body subjected to water-repellent finishing also corresponds to the “electrode substrate”. (A carbon fiber fired body that is not subjected to water repellent treatment naturally corresponds to an “electrode substrate”).

<Formation of microporous part [A] and microporous part [B]>
The microporous portion [A] is formed by applying a carbon coating liquid [A], which is a mixture of the hydrophobic resin used in the above-described water-repellent processing and the carbonaceous powder, on one surface of the electrode substrate, The microporous part [B] is obtained by applying the carbon coating liquid [B], which is a mixture of the hydrophobic resin used in the above-described water-repellent processing and the carbonaceous powder, to the other side of the electrode substrate. Can be formed. The carbon coating solution [A] and the carbon coating solution [B] may be the same type or different types.

  Thereby, the gas diffusion electrode base material of the present invention includes the microporous part [A], the electrode base material, and the microporous part [B] arranged in this order.

  The carbon coating solution [A] and the carbon coating solution [B] may contain a dispersion medium such as water or an organic solvent, or may contain a dispersion aid such as a surfactant. Water is preferable as the dispersion medium, and a nonionic surfactant is more preferably used as the dispersion aid.

  The coating of the carbon coating liquid onto the electrode substrate can be performed using various commercially available coating apparatuses. As the coating method, screen printing, rotary screen printing, spray spraying, intaglio printing, gravure printing, die coater coating, bar coating, blade coating and the like can be used, but in order to form the microporous portion [A]. The pattern coating is preferably screen printing (including rotary screen printing) or gravure printing. That is, in the present invention, the microporous portion [A] is preferably formed by screen printing or gravure printing. Among these, screen printing is preferable because the carbon coating liquid [A] can be applied in a large amount to the electrode substrate and the amount can be easily adjusted as compared with other methods. When performing pattern coating of the carbon coating liquid [A] on the electrode substrate by screen printing, a photosensitive paint is applied on the screen printing plate, and a portion other than the desired pattern is cured, and an uncured pattern portion By removing the resin, a screen printing plate having a pattern is prepared and applied.

  Among the screen printing, the carbon coating liquid [A] can be continuously applied to the electrode base material, and therefore, the rotary screen printing is preferable as the coating method.

  The mesh, aperture ratio, aperture, and thickness of the rotary screen plate are appropriately selected according to the viscosity characteristics of the carbon coating liquid [A] to be used.

  In the rotary screen printing, the printing speed is preferably 0.5 to 15 m / min. When the printing speed is 0.5 m / min or more, the productivity is improved and the cost of the gas diffusion electrode substrate can be reduced. Further, the printing accuracy is improved by being 15 m / min or less.

  On the other hand, in the coating of the carbon coating solution [B], a die coater coating is preferable because the coating amount can be quantified regardless of the surface roughness of the electrode substrate.

  The coating methods exemplified above are only for illustrative purposes and are not necessarily limited to these.

  As a method for forming the microporous portion [A] and the microporous portion [B], one surface of the electrode base material is coated with a predetermined carbon coating liquid to obtain a coated material, A method of drying the coating liquid at a temperature of 120 ° C. is preferred.

  That is, it is preferable that the coated material is put into a drier set at a temperature of 80 to 120 ° C. and dried for 5 to 30 minutes. The amount of drying air may be determined as appropriate, but rapid drying is undesirable because it may induce micro cracks on the surface. The dried coating is put into a muffle furnace, a baking furnace or a high-temperature dryer, heated at 300 to 380 ° C. for 5 to 20 minutes to melt the hydrophobic resin, and the carbonaceous powders are bonded to each other. It is preferable to form a microporous part [A] and a microporous part [B].

<Membrane electrode assembly>
The membrane electrode assembly of the present invention is a membrane assembly having a catalyst layer on both sides of an electrolyte membrane and further having a gas electrode substrate on the outside (both outside) of the catalyst layer, the gas electrode substrate At least one of the above is the gas electrode substrate described above. A configuration example of the membrane electrode assembly of the present invention is shown in FIG. Thus, in this invention, a membrane electrode assembly can be comprised by joining the above-mentioned gas diffusion electrode base material to at least one side of the solid polymer electrolyte membrane which has a catalyst layer on both surfaces. Moreover, in the membrane electrode assembly of the present invention, it is particularly preferable that both of the gas electrode substrates provided on both outer sides of the catalyst layer are the above-described gas electrode substrate of the present invention.

  Further, in the membrane electrode assembly of the present invention, the membrane electrode assembly may be configured such that the microporous portion [B] is disposed on the catalyst layer side, that is, the microporous portion [B] is in contact with the catalyst layer. preferable. FIG. 16 shows a configuration example in which the microporous portion [B] of the gas diffusion electrode substrate is in contact with the catalyst layer.

  Since the microporous part [B] having a large area ratio is on the electrolyte membrane side, the reverse diffusion of generated water is more likely to occur, and the microporous part [A] having a small area ratio is on the separator side. Flooding can be suppressed without impeding drainage from the electrode substrate. That is, when the microporous part [B] is on the separator side, the drainage from the gas diffusion electrode base material is deteriorated, so the microporous part [A] is preferably arranged on the separator side. Further, the microporous part [B] having a large area ratio of the microporous part is arranged on the catalyst layer side, so that the contact area between the catalyst layer and the gas diffusion electrode substrate is increased, and the contact electrical resistance is reduced. it can.

  In the membrane electrode assembly of the present invention, it is preferable that both of the gas diffusion electrode substrates provided on both outer sides of the catalyst layer are the above-described gas diffusion electrode substrates of the present invention. It is particularly preferable that both of the microporous parts [B] are in contact with the catalyst layer.

<Fuel cell>
The fuel cell of the present invention has separators on both sides of the above-described membrane assembly (a configuration example of the fuel cell of the present invention is shown in FIG. 16). That is, a fuel cell is constituted by having separators on both sides of the membrane electrode assembly. Usually, a polymer electrolyte fuel cell is constructed by laminating a plurality of such membrane electrode assemblies on both sides sandwiched by a separator through a gasket. The catalyst layer is composed of a layer containing a solid polymer electrolyte and catalyst-supporting carbon. As the catalyst, platinum is usually used. In a fuel cell in which a reformed gas containing carbon monoxide is supplied to the anode side, it is preferable to use platinum and ruthenium as the catalyst on the anode side. As the solid polymer electrolyte, it is preferable to use a perfluorosulfonic acid polymer material having high proton conductivity, oxidation resistance, and heat resistance. Such a fuel cell unit and the configuration of the fuel cell itself are well known.

  In the fuel cell of the present invention, the microporous portion [B] of the gas diffusion electrode substrate is preferably in contact with the catalyst layer.

  Hereinafter, the present invention will be described specifically by way of examples. The electrode substrate used in the examples, the method for producing the gas diffusion electrode substrate, and the cell performance evaluation method for the fuel cell are shown below.

<Preparation of electrode substrate>
Polyacrylonitrile-based carbon fiber “Torayca (registered trademark)” T300 (average carbon fiber diameter: 7 μm) manufactured by Toray Industries, Inc. was cut to an average length of 12 mm, dispersed in water, and continuously made by wet paper making. . Further, a 10% by mass aqueous solution of polyvinyl alcohol as a binder was applied to the paper and dried to prepare a paper body having a carbon fiber basis weight of 15.5 g / m ² . The coating amount of polyvinyl alcohol was 22 parts by mass with respect to 100 parts by mass of the papermaking body.

  A thermosetting resin using a resin in which a resol type phenolic resin and a novolac type phenolic resin are mixed at a weight ratio of 1: 1 as a thermosetting resin, scaly graphite (average particle size 5 μm) as a carbon filler, and methanol as a solvent. / Carbon-based filler / solvent = 10 parts by mass / 5 parts by mass / 85 parts by mass These were mixed and stirred for 1 minute using an ultrasonic dispersion device to obtain a uniformly dispersed resin composition. .

  The paper body cut into 15 cm × 12.5 cm is immersed in a resin composition filled with aluminum bat, and the resin component (thermosetting resin + carbon filler) becomes 130 parts by mass with respect to 100 parts by mass of the carbon fibers. After impregnating in this manner, it was dried by heating at 100 ° C. for 5 minutes to prepare a pre-impregnated body. Next, it heat-processed for 5 minutes at 180 degreeC, pressing with a flat plate press. In addition, a spacer was disposed on the flat plate press during the pressurization, and the interval between the upper and lower press face plates was adjusted so that the thickness of the pre-impregnated body after the heat treatment was 130 μm.

  The base material obtained by heat-treating the pre-impregnated body was introduced into a heating furnace having a maximum temperature of 2400 ° C. maintained in a nitrogen gas atmosphere in a heating furnace to obtain a carbon fiber fired body.

  5 parts by mass of PTFE resin was applied to 95 parts by mass of the carbon fiber fired body, heated at 100 ° C. for 5 minutes and dried to prepare an electrode substrate having a thickness of 100 μm.

<Formation of microporous part [A] and microporous part [B]>
In order to form the microporous portion [A], a pattern-like carbon coating liquid portion was formed on one surface (A surface) of the electrode base material using a screen printing plate in which a portion other than the pattern portion was masked with a resin. The carbon coating liquid used here includes acetylene black (“DENKA BLACK (registered trademark)” manufactured by Denki Kagaku Kogyo Co., Ltd.) and PTFE resin (“POLYFLON (registered trademark)” D-1E manufactured by Daikin Industries, Ltd.) as carbon black. ), Surfactant (“TRITON (registered trademark)” X-100 manufactured by Nacalai Tesque Co., Ltd.), purified water, carbon black / PTFE resin / surfactant / purified water = 7.7 parts by mass / 2.5 What mixed these by the compounding ratio of the mass part / 14 mass parts / 75.8 mass parts was used. After heating the electrode base material on which the pattern-like carbon coating liquid portion is formed at 120 ° C. for 10 minutes, the surface (A surface) having the pattern-like carbon coating liquid portion is formed in order to form the microporous portion [B]. On the opposite side, the carbon coating solution was applied using a coater (die coater) and heated at 120 ° C. for 10 minutes. The heated coating material is heated at 380 ° C. for 10 minutes to prepare a gas diffusion electrode substrate having a microporous portion [A] on the surface of the electrode substrate and a microporous portion [B] on the other surface. Produced.

  In other words, since the microporous portion is formed by applying the carbon coating liquid to the electrode substrate and heating it, one of the electrode substrates is formed so that the microporous portion [A] forms a desired pattern. A carbon coating solution was applied to the surface (side A). In other words, the carbon coating liquid is applied to the part where the microporous part is formed on the electrode base material, while the carbon coating liquid is applied to the part where the microporous part is not formed on the electrode base material. In order to avoid this, a carbon coating solution was applied onto the electrode substrate using a screen printing plate. More specifically, a screen printing plate partially covered with a resin (masked) was used so that the carbon coating liquid was not applied to the portion where the microporous portion was not formed on the electrode substrate. After coating, the carbon coating solution was heated. Subsequently, a carbon coating solution was applied to the other surface (side B) of the electrode substrate (in the case of forming a pattern on the microporous portion [B], the above-described microporous portion [A] The same method as the forming method can be taken). After coating, this is heated to produce a gas diffusion electrode substrate having a microporous portion [A] on one surface of the electrode substrate and a microporous portion [B] on the other surface (B surface). did.

<Evaluation of power generation performance of polymer electrolyte fuel cells>
1.00 g of platinum-supported carbon (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., platinum support: 50% by mass), 1.00 g of purified water, “Nafion (registered trademark)” solution (“Nafion (registered trademark)” 5 manufactured by Aldrich) (0.0 mass%) 8.00 g and isopropyl alcohol (manufactured by Nacalai Tesque) 18.00 g were sequentially added to prepare a catalyst solution.

Next, “Naflon (registered trademark)” PTFE tape “TOMBO (registered trademark)” No. 7 cut to 7 cm × 7 cm was used. A catalyst solution was applied to 9001 (manufactured by NICHIAS Corporation) by spraying and dried at room temperature to prepare a PTFE sheet with a catalyst layer having a platinum amount of 0.3 mg / cm ² . Subsequently, a solid polymer electrolyte membrane “Nafion (registered trademark)” NRE-211CS (manufactured by DuPont) cut to 10 cm × 10 cm is sandwiched between two PTFE sheets with a catalyst layer, and pressed to 5 MPa with a flat plate press. Pressing at 5 ° C. for 5 minutes transferred the catalyst layer to the solid polymer electrolyte membrane. After pressing, the PTFE sheet was peeled off to produce a solid polymer electrolyte membrane with a catalyst layer.

  Next, the solid polymer electrolyte membrane with a catalyst layer is sandwiched between two gas diffusion electrode substrates cut to 7 cm × 7 cm, and pressed at 130 ° C. for 5 minutes while being pressurized to 3 MPa with a flat plate press, and a membrane electrode assembly Was made. The gas diffusion electrode base material was arranged so that the surface having the microporous portion [B] was in contact with the catalyst layer side.

  The obtained membrane electrode assembly was incorporated into a single cell for fuel cell evaluation, and the voltage when the current density was changed was measured. Here, as the separator, a serpentine type single groove having a groove width of 1.5 mm, a groove depth of 1.0 mm, and a rib width of 1.1 mm was used. Further, evaluation was performed by supplying hydrogen pressurized to 210 kPa to the anode side and air pressurized to 140 kPa to the cathode side. Both hydrogen and air were humidified using a humidification pot set at 70 ° C. The utilization rates of hydrogen and oxygen in the air were 80% and 67%, respectively.

First, when the operating temperature was set to 65 ° C. and the current density was set to 2.2 A / cm ² , the output voltage was measured and used as an index of flooding resistance (low temperature performance). In addition, when the operating temperature was set to 65 ° C. and the current density was set to 2.2 A / cm ² and held for 30 minutes, the number of output voltage drops was counted and used as an index of plugging resistance. That is, the number of times that the output voltage becomes 0.2V or less in 30 minutes is counted, C is 7 times or more, B is 5-6 times, A is 3-4 times, 2 times. The following was designated S. Next, the current density is set to 1.2 A / cm ² , the operating temperature is maintained from 80 ° C. for 5 minutes, the output voltage is measured while repeatedly increasing 2 ° C. over 5 minutes, and the limit temperature at which power generation is possible is obtained. It was used as an index of dry-up resistance (high temperature performance).

Example 1
The microporous portion [A] of Example 1 uses a screen plate so as to have a lattice-like pattern (a lattice shape represented by FIG. 1) composed of straight lines having a line width of 0.5 mm and a line interval of 0.7 mm. Made. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. When the area ratio of the microporous portion [A] of this gas diffusion electrode substrate was measured, it was 66%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.35 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 91 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described above, both flooding resistance and dry-up resistance were good. Moreover, the coating speed of the carbon coating liquid for forming the microporous portion [A] onto the electrode substrate could be increased to 1 m / min.

(Example 2)
The microporous part [A] of Example 2 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.1 mm and a line interval of 1.8 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. When the area ratio of the microporous part [A] of this gas diffusion electrode substrate was measured, it was 10%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was good. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 90 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described above, both flooding resistance and dry-up resistance were good.

Example 3
The microporous part [A] of Example 3 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was measured and found to be 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described above, both flooding resistance and dry-up resistance were good.

Example 4
The microporous part [A] of Example 4 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.3 mm and a line interval of 1.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was measured and found to be 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described above, both flooding resistance and dry-up resistance were good.

(Example 5)
The microporous part [A] of Example 5 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.3 mm and a line interval of 6 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. When the area ratio of the microporous part [A] of this gas diffusion electrode substrate was measured, it was 9.3%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was good. The output voltage is 0.39 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 91 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described above, both flooding resistance and dry-up resistance were good.

(Example 6)
The microporous part [A] of Example 6 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.7 mm. The microporous portion [B] was prepared using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous part [A] of this gas diffusion electrode substrate was 66%, and the area ratio of the microporous part [B] was 92%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.35 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 90 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described above, both flooding resistance and dry-up resistance were good.

(Example 7)
The microporous part [A] of Example 7 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.7 mm. The microporous portion [B] was prepared using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. When producing the membrane electrode assembly, the gas diffusion electrode substrate was disposed so that the surface having the microporous portion [A] was in contact with the catalyst layer side. The area ratio of the microporous part [A] of this gas diffusion electrode substrate was 66%, and the area ratio of the microporous part [B] was 92%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.33 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 90 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described in the above, the dry-up resistance was good, but compared with Example 6, the flooding resistance was slightly lowered.

(Example 8)
The microporous part [A] of Example 8 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.1 mm and a line interval of 0.4 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was good. The output voltage is 0.39 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described above, both flooding resistance and dry-up resistance were good.

Example 9
The microporous part [A] of Example 9 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 3 mm and a line interval of 12 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was good. The output voltage is 0.36 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described above, both flooding resistance and dry-up resistance were good.

(Example 10)
The microporous part [A] of Example 10 was produced using a screen plate so as to form a stripe pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.9 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described above, both flooding resistance and dry-up resistance were good.

(Example 11)
The microporous portion [A] of Example 11 was produced using a screen plate so as to form an island-like pattern (a shape represented by FIG. 11) having a vertical and horizontal width of 0.5 mm and an interval of 0.33 mm. . Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the resistance to plugging was slightly lowered. The output voltage is 0.36 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described above, both flooding resistance and dry-up resistance were good.

(Example 12)
The microporous portion [A] of Example 12 was produced using a screen plate so as to have a random shape (a shape represented by FIG. 10) including a portion having a line width smaller than 0.1 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the resistance to plugging was slightly lowered. The output voltage is 0.35 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 91 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described in the above, the flooding resistance was slightly lowered and the dry-up resistance was good.

(Example 13)
The microporous part [A] of Example 13 was produced using a screen plate so as to form a stripe pattern composed of straight lines having a line width of 0.1 mm and a line interval of 0.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous part [A] of this gas diffusion electrode substrate was 33%. As a result of evaluating the power generation performance of the gas diffusion electrode substrate, the plugging resistance was a little fixed. The output voltage is 0.36 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described in the above, both flooding resistance and dry-up resistance were favorable.

(Example 14)
The microporous part [A] of Example 14 was produced using a screen plate so as to form a stripe pattern composed of straight lines having a line width of 0.3 mm and a line interval of 0.5 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 38%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described above, both flooding resistance and dry-up resistance were good.

(Example 15)
The microporous part [A] of Example 15 was produced using a screen plate so as to form a stripe pattern composed of straight lines having a line width of 10 mm and a line interval of 18 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the resistance to plugging was slightly lowered. The output voltage is 0.35 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 91 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described above, both flooding resistance and dry-up resistance were good.

(Example 16)
The microporous part [A] of Example 16 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.3 mm and a line interval of 2.0 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. When the area ratio of the microporous portion [A] of this gas diffusion electrode substrate was measured, it was 24%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.39 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 2 As described above, both flooding resistance and dry-up resistance were good.

(Example 17)
The microporous part [A] of Example 17 was produced using a rotary screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.3 mm and a line interval of 2.0 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. When the area ratio of the microporous portion [A] of this gas diffusion electrode substrate was measured, it was 24%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.39 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 3 As described in 1., both flooding resistance and dry-up resistance were good. Moreover, the coating speed of the carbon coating liquid for forming the microporous portion [A] onto the electrode substrate could be increased to 5 m / min.

(Example 18)
The microporous part [A] of Example 18 was produced using a rotary screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.3 mm and a line interval of 1.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was measured and found to be 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 92 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 3 As described in 1., the flooding resistance, the dry-up resistance, and the coating speed of the microporous part [A] were all good. Moreover, the coating speed of the carbon coating liquid for forming the microporous portion [A] onto the electrode substrate could be increased to 5 m / min.

(Example 19)
The microporous part [A] of Example 19 was prepared by gravure printing so as to be a lattice-like pattern composed of straight lines having a line width of 0.3 mm and a line interval of 1.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was measured and found to be 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was good. The output voltage is 0.36 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 91 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 3 As described in the above, both the flooding resistance and the dry-up resistance were good. Moreover, the coating speed of the carbon coating liquid for forming the microporous part [A] onto the electrode substrate could be increased to 2 m / min.

(Example 20)
The microporous part [A] of Example 20 was produced using a screen plate so as to form a stripe pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.9 mm. The microporous portion [B] was prepared using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous part [A] of this gas diffusion electrode substrate was 36%, and the area ratio of the microporous part [B] was 92%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 90 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 3 As described above, both flooding resistance and dry-up resistance were good.

(Example 21)
The microporous part [A] of Example 21 was produced using a screen plate so as to form a stripe pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.9 mm. The microporous portion [B] was prepared using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. When the membrane / electrode assembly was produced, the gas diffusion electrode substrate was placed so that the surface having the microporous portion [A] was in contact with the catalyst layer side. The area ratio of the microporous part [A] of this gas diffusion electrode substrate was 36%, and the area ratio of the microporous part [B] was 92%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.33 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 89 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 1 As described in the above, the dry-up resistance was good, but the flooding resistance was slightly lowered as compared with Example 20.

  The evaluation result in an Example etc. are put together in Tables 1-3, and are shown.

(Comparative Example 1)
The electrode substrate of Comparative Example 1 was not provided with the microporous portion [A]. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the resistance to plugging was greatly reduced. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 88 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 4 As described above, the flooding resistance was good, but the dry-up resistance was lowered.

(Comparative Example 2)
The microporous part [A] of Comparative Example 2 was produced using a coater (die coater) so as to be planar. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 100%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the output voltage could not be taken out (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 89 ° C. (humidification temperature 70 ° C., Current density was 1.2 A / cm ² ), and as shown in Table 4, both flooding resistance and dry-up resistance were reduced. The reason why the high-temperature performance is low is that the area ratio of the microporous portion [A] is high, so that the gas diffusion electrode base material has low surface gas diffusibility, and fuel cannot be sufficiently supplied to the catalyst. Moreover, since the area ratio of the microporous part [A] is high, the drainage performance is lowered, causing flooding inside the electrode base material and lowering the low temperature performance. In addition, the coating speed to the electrode base material of the carbon coating liquid for forming microporous part [A] was able to be accelerated to 2 m / min.

(Comparative Example 3)
The microporous part [A] of Comparative Example 3 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 0.5 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous part [A] of this gas diffusion electrode substrate was 75%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was extremely good. The output voltage is 0.25 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 88 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 4 As described in 1., both the flooding resistance and the dry-up resistance decreased. The reason why the high-temperature performance is low is that the area ratio of the microporous portion [A] is high, so that the gas diffusion electrode base material has low surface gas diffusibility, and fuel cannot be sufficiently supplied to the catalyst. Moreover, since the area ratio of the microporous part [A] is high, the drainage performance is lowered, causing flooding inside the electrode base material and lowering the low temperature performance.

(Comparative Example 4)
The microporous part [A] of Comparative Example 4 was produced using a screen plate so as to form a lattice pattern composed of straight lines having a line width of 0.5 mm and a line interval of 20 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] of this gas diffusion electrode substrate was 4.8%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the plugging resistance was greatly reduced. This is because the area ratio of the microporous portion [A] is small and liquid water does not easily stay in the flow path. The output voltage is 0.38 V (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 88 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ), Table 4 As described above, the flooding resistance was good, but the dry-up resistance was lowered.

(Comparative Example 5)
The electrode substrate of Comparative Example 5 was not provided with the microporous portion [A]. The microporous portion [B] was prepared using a screen plate having a grid pattern composed of straight lines having a line width of 0.5 mm and a line interval of 2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous part [B] of this gas diffusion electrode substrate was 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the output voltage could not be taken out (operation temperature 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 85 ° C. (humidification temperature 70 ° C., Current density was 1.2 A / cm ² ), and as shown in Table 4, both flooding resistance and dry-up resistance were reduced. The low temperature performance is low because the area ratio of the microporous portion [B] is low, the contact area with the catalyst layer is low, and the contact electrical resistance is large, and the high temperature performance is low for the microporous portion [B]. This is because, since the area ratio is low, water vapor easily escapes to the separator side, and drying of the electrolyte membrane becomes remarkable.

(Comparative Example 6)
The microporous part [A] of Comparative Example 6 was produced using a screen plate so as to be a lattice-like pattern composed of straight lines having a line width of 0.5 mm and a line interval of 2 mm. The microporous portion [B] was also produced using a screen plate having a grid pattern composed of straight lines having a line width of 0.5 mm and a line interval of 2 mm. Other than that, a gas diffusion electrode substrate was obtained in the same manner as described in <Preparation of electrode substrate> and <Formation of microporous portion [A] and microporous portion [B]>. The area ratio of the microporous portion [A] and the microporous portion [B] of this gas diffusion electrode substrate is 36%. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, the output voltage cannot be extracted (operation) 65 ° C., humidification temperature 70 ° C., current density 2.2 A / cm ² ), limit temperature 85 ° C. (humidification temperature 70 ° C., current density 1.2 A / cm ² ). Both flooding and dry-up resistance decreased. The low temperature performance is low because the area ratio of the microporous portion [B] is low, the contact area with the catalyst layer is low, and the contact electrical resistance is large, and the high temperature performance is low for the microporous portion [B]. This is because, since the area ratio is low, water vapor easily escapes to the separator side, and drying of the electrolyte membrane becomes remarkable.

  Table 4 summarizes the evaluation results of the comparative examples.

1: Electrode base material 2: Microporous part [A]
3: Microporous part [B]
4: Microporous part 41: Microporous part 5: Gas diffusion electrode substrate 6. electrolyte membrane Catalyst layer 8. 8. Membrane electrode assembly Separator 10. Fuel cell

Claims (9)

The microporous part [A], the electrode substrate, and the microporous part [B] are arranged in this order, and the area ratio of the microporous part [A] is in the range of 5 to 70%. Ri range der area ratio of 80% to 100% of [B], the microporous portion [a] is the gas diffusion electrode substrate for a fuel cell which is characterized that you have to form a pattern.
However, the area ratio is the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate. The microporous part [A], the electrode substrate, and the microporous part [B] are arranged in this order, and the area ratio of the microporous part [A] is in the range of 5 to 70%. The area ratio of [B] is in the range of 80 to 100%, and the microporous portion [A] is formed by providing a large number of microporous portions on the surface of the electrode substrate. Gas diffusion electrode base material for fuel cells.
However, the area ratio is the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate. The microporous part [A], the electrode substrate, and the microporous part [B] are arranged in this order, and the area ratio of the microporous part [A] is in the range of 5 to 70%. A fuel cell gas diffusion electrode substrate, wherein the area ratio of [B] is in the range of 80 to 100%, and the microporous portion [A] has a random shape.
However, the area ratio is the ratio (%) of the area covered with the microporous portion to the area of the electrode substrate. The gas diffusion electrode substrate for a fuel cell according to any one of claims 1 to 3, wherein the microporous part [A] is composed of an assembly of linear microporous parts having an average line width of 0.1 to 5 mm. The gas diffusion electrode substrate for a fuel cell according to claim 1 or 2 , wherein the microporous portion [A] has a stripe shape or a lattice shape. A method for producing a fuel cell gas diffusion electrode substrate according to any one of claims 1 to 5 , wherein the microporous portion [A] is formed by screen printing or gravure printing. A method of manufacturing the material. A membrane electrode assembly having a catalyst layer on both sides of an electrolyte membrane and further having a gas diffusion electrode substrate outside the catalyst layer, wherein at least one of the gas diffusion electrode substrates is any one of claims 1 to 5 . A membrane electrode assembly, which is the gas diffusion electrode substrate according to claim 1. The membrane electrode assembly according to claim 7 , wherein the microporous portion [B] of the gas diffusion electrode substrate is in contact with the catalyst layer. The fuel cell which has a separator on both sides of the membrane electrode assembly of Claim 8 .

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